WO2009096571A1 - Novel compound, method of synthesis thereof, and oil additive - Google Patents

Abstract

A novel compound is provided which, when used as an additive for a fluorochemical oil, has the effect of preventing the fluorochemical oil from being pyrolyzed. The compound is represented by the following general formula (1). [In the formula, Y represents oxygen (O), sulfur (S), CO, SO, or SO2; k is an integer of 1-5; m is an integer of 1-10; n is an integer of 1 or larger; and the positions of the two substituents bonded to each phenyl group may be any of ortho, meta, and para.]

Description

Novel compound, synthesis method thereof and oil additive

The present invention relates to a novel compound which can be used as an oil additive excellent in the thermal decomposition resistance of a fluorine-based oil, a synthesis method thereof and an oil additive.

In general, oil additives are added to oils for the purpose of performance addition and performance improvement such as wear resistance, durability, heat resistance, rust resistance and the like.

Therefore, not only the development of oil but also the development of oil additives is an important issue, and in order to achieve the above-mentioned purpose, novel compounds and novel synthetic methods thereof are being studied.

The present inventors focused attention on the additive of the fluorinated oil among the oils, and as a result of continuing research on various additives, the polyether part of the fluorinated oil is thermally decomposed, and hence the fluorinated oil It has been found that the heat resistance is insufficient.

Then, when research was continued about the method of preventing the thermal decomposition of a fluorine-type oil, when a certain specific compound was used as an oil additive, it discovered that the thermal-degradation prevention performance effect of a fluorine-type oil was exhibited.

In addition, although the antifoamer of m = 0 is disclosed by patent document 1 in General formula (1), when it uses as an additive of fluorine-type oil, the thermal decomposition prevention performance of fluorine-type oil is There is an inferior problem.
Japanese Patent Application Laid-Open No. 59-12708

Then, the subject of this invention makes it a subject to provide the novel compound which exhibits the thermal decomposition prevention performance effect of this fluorine-type oil, when it uses as an additive of fluorine-type oil.

Moreover, the subject of this invention makes it a subject to provide the oil additive which exhibits the thermal decomposition prevention performance effect of fluorine-type oil.

Furthermore, another object of the present invention is to provide a synthesis method of a novel compound synthesized using a substance having hydrogen fluoride trapping ability similar to that of sodium fluoride and less toxic than sodium fluoride. Do.

Furthermore, other objects of the present invention will become apparent from the following description.

The above problems are solved by the following inventions.

〔式中、Ｙは酸素原子（Ｏ）、硫黄原子（Ｓ）、ＣＯ基、ＳＯ基又はＳＯ_２基を表わし、ｋは１～５の整数であり、ｍは１～１０の整数であり、ｎは１以上の整数である。フェニル基に有する２つの置換基の置換位置は、オルト位、メタ位、パラ位の何れでも良い。〕 The invention according to claim 1 is a compound represented by the following general formula (1).
General formula (1)

[Wherein, Y represents an oxygen atom (O), a sulfur atom (S), a CO group, an SO group or an SO ₂ group, k is an integer of 1 to 5, and m is an integer of 1 to 10, n is an integer of 1 or more. The substitution position of the two substituents on the phenyl group may be any of ortho, meta and para positions. ]

The invention according to claim 2 is the compound according to claim 1, wherein in the general formula (1), Y is an oxygen atom (O) and m is 1 or 2.

The invention according to claim 3 is an oil additive represented by the following general formula (1) (hereinafter referred to as the oil additive of the present invention).
General formula (1)
[Wherein, Y represents an oxygen atom (O), a sulfur atom (S), a CO group, an SO group or an SO ₂ group, k is an integer of 1 to 5, and m is an integer of 1 to 10, n is an integer of 1 or more. The substitution position of the two substituents on the phenyl group may be any of ortho, meta and para positions. ]

The invention according to claim 4 is the oil additive according to claim 3, wherein in the general formula (1), Y is an oxygen atom (O) and m is 1 or 2.

The invention according to claim 5 is the oil additive according to claim 3 or 4, which is an additive of a fluorine-based oil.

　〔式中、ｋは１～５の整数であり、ｎは１以上の整数である。〕
　一般式（３）

〔式中、Ｙは酸素原子（Ｏ）、硫黄原子（Ｓ）、ＣＯ基、ＳＯ基又はＳＯ_２基を表わし、ｍは１～１０の整数である。フェニル基に有する２つの置換基の置換位置は、オルト位、メタ位、パラ位の何れでも良い。〕 In the invention according to claim 6, the acid fluoride compound represented by the following general formula (2) and the compound having a diamino group represented by the following general formula (3) are reacted in a pyridine solvent to obtain It is a synthetic method characterized by synthesizing a compound represented by the general formula (1).
General formula (2)

[Wherein, k is an integer of 1 to 5 and n is an integer of 1 or more. ]
General formula (3)

[Wherein, Y represents an oxygen atom (O), a sulfur atom (S), a CO group, an SO group or an SO ₂ group, and m is an integer of 1 to 10. The substitution position of the two substituents on the phenyl group may be any of ortho, meta and para positions. ]

　〔式中、ｎは１以上の整数である。〕 The invention according to claim 7 is the synthetic method according to claim 6, wherein the acid fluoride body represented by the general formula (2) is an acid fluoride body represented by the following general formula (4).
General formula (4)

[Wherein, n is an integer of 1 or more. ]

ADVANTAGE OF THE INVENTION According to this invention, when it uses as an additive of fluorine-type oil, the novel compound which exhibits the thermal decomposition prevention performance effect of this fluorine-type oil can be provided.

Further, according to the present invention, it is possible to provide an oil additive which exhibits the thermal decomposition preventing effect of the fluorinated oil by using it as an additive of the fluorinated oil.

Furthermore, according to the present invention, it is possible to provide a synthesis method of a novel compound synthesized using a substance having hydrogen fluoride trapping ability similar to that of sodium fluoride and less toxic than sodium fluoride.

Graph showing the result of Comparative Example 1 Graph showing the results of Example 1 Graph showing the results of Example 2 Graph showing the results of Example 3 Graph showing the results of Example 4 Graph showing the result of Comparative Example 2

Hereinafter, embodiments of the present invention will be described.

<New compound>
The novel compound according to the present invention is a compound represented by the following general formula (1).

　 General formula (1)

In the formula, Y represents an oxygen atom (O), a sulfur atom (S), a CO group, an SO group or an SO ₂ group, preferably an oxygen atom (O).

K is an integer of 1 to 5, preferably 2 or 3.

M is an integer of 1 to 10, preferably in the range of 1 to 5, and more preferably 1 or 2.

N is an integer of 1 or more, preferably in the range of 1 to 40.

The substitution position of the two substituents on the phenyl group may be any of ortho, meta and para positions.

The method for synthesizing the novel compound according to the present invention can be incorporated into the description described in detail below, and its application can be suitably used as an additive of a fluorine-based oil, and when added to a fluorine-based oil, a fluorine-based oil It has the effect of preventing the thermal decomposition of oil.

<New synthesis method>
The synthesis method according to the present invention comprises an acid fluoride body represented by the following general formula (2), preferably an acid fluoride body represented by the following general formula (4), and a diamino group represented by the following general formula (3) The present invention is characterized in that the compound is reacted in a pyridine solvent to synthesize the compound represented by the general formula (1) according to claim 1.

General formula (2)

In the formula, k is an integer of 1 to 5, and n is an integer of 1 or more.

General formula (4)

In the formula, n is an integer of 1 or more, preferably in the range of 1 to 40.

General formula (3)

In the formula, Y represents an oxygen atom (O), a sulfur atom (S), a CO group, an SO group or an SO ₂ group, preferably an oxygen atom (O).

M is an integer of 1 to 10, preferably in the range of 1 to 5, and more preferably 1 or 2.

The substitution position of the two substituents on the phenyl group may be any of ortho, meta and para positions.

Since the synthesis method according to the present invention uses a low-toxic substance (pyridine) having the same hydrogen fluoride trapping ability as sodium fluoride in order to carry out the reaction in a pyridine solvent, such as sodium fluoride No problem.

Pyridine toxicity and properties are as follows.

Oral rat toxicity: LD50 890 mg / kg
Liquid at normal temperature (melting point-42 ° C, boiling point 115.5 ° C)

The pyridine which is the solvent of the present invention does not have to be a single substance, and other organic solvents may be used in combination to improve the solubility of the raw material compound and the reaction product.

Examples of the compound having a diamino group represented by the general formula (3) include 1,4-bis (4-aminophenoxy) benzene and the like, and such 1,4-bis (4-aminophenoxy) benzene is exemplified by CAS No. . 10526-07-5, 2479-46-1, 3491-12-1, etc.

The compound having a diamino group described above may be an aromatic polyether having m = 2 or more, and further, a compound in which each ether bond atom O (oxygen atom) is replaced by CO, S, SO, SO ₂ (eg, CAS No. 141699-34-5, 60191-34-6, 17619-11-3).

The above synthesis method is a method in the case where k is 3 in the compound represented by the general formula (1), but the compound can be similarly synthesized using acid fluorides having different k. Also in that case, it is important to use a pyridine solvent.

Here, Patent Document 1 (JP-A-59-12708) describes a synthesis example of a fluorinated ether aromatic diamide compound as an antifoaming agent. That is, using sodium fluoride, an acid fluoride of a poly (perfluoroether) compound is reacted with p, p'-diaminodiphenyl ether to synthesize a compound having a diamide group (hereinafter, a diamide). And the example which the following diamide I is synthesize | combined is disclosed by the reference example 13 of the said patent document 1 using p, p'- diamino diphenyl ether of following structural formula.

(P, p'-diaminodiphenyl ether)

(Diamide I)

In the reaction using the acid fluoride body, not only in Patent Document 1 described above, hydrogen fluoride which is a toxic substance is by-produced, but sodium fluoride is frequently used as a trapping agent.

However, the sodium fluoride is an acute toxic substance (oral rat LD50 180 mg / kg). Furthermore, due to its form of powder, it is easy to scatter and float, and if it adheres to the skin or mucous membrane, it has a risk of causing permanent injury, and sodium fluoride has a handling problem.

As an exemplary compound of the novel compound according to the present invention or the novel compound synthesized by the novel synthesis method according to the present invention, in the general formula (1), k = 3, m = 1, n = 1 and Y is an oxygen atom, Compounds in which the substitution position is the para position (exemplified compound 1-1), in the general formula (1), k = 3, m = 1, n = 11, Y is an oxygen atom, and the substitution position is the compound in the para position (exemplified compound 1-2) In the general formula (1), k = 3, m = 1, n = 40, Y is an oxygen atom, and the substitution position is a compound at the para position (exemplified compound 1-3) in the general formula (1) And k = 3, m = 2, n = 1, and Y are oxygen atoms, and the substitution position is a compound at the para position (exemplified compound 1-4).

<Oil additive>
The oil additive of the present invention can be added to various base oils (oils), but when added to a fluorine-based oil, it has an effect of preventing the thermal decomposition of the fluorine-based oil.

The fluorine-based oil is not particularly limited, and known oils can be used.

In the general formula (1), the value of n is related to the affinity and solubility with the base oil, and when n = 0, when the composition represented by the general formula (1) is added to the oil, The problem of not dissolving in base oil arises.

In addition, the value of m is involved in suppressing the decomposition of the polyether (ether bond) of the fluorine-based oil, and when m = 0, fluorine is used when used at high temperature (for example, in the range of 400 to 430 ° C.) The polyether (ether bond) of the oil based system is decomposed. That is, in the case of m = 0, there arises a problem that the fluorine-based oil is thermally decomposed.

Although the antifoamer of m = 0 is disclosed by patent document 1 (Unexamined-Japanese-Patent No. 59-12708), even if it uses this as a fluorine-type oil additive, for example, the thermal decomposition prevention performance of this fluorine-type oil However, the effect of the present invention can not be exhibited.

The blending ratio in the case of adding the oil additive of the present invention to the fluorinated oil is preferably in the range of 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the base oil. It is a range.

The present invention will be described in more detail by the following examples, but the present invention is not limited thereto.

Synthesis Example 1
Synthesis of exemplified compound 1-1 (in the general formula (1), k = 3, m = 1, n = 1, Y is an oxygen atom, and the substitution position is para)

Dissolve 29.5 g of 1,4-bis (41-aminophenoxy) benzene in 200 mL of pyridine, slowly add 124 g of acid fluoride (n = 1) slowly on an ice bath, and stir overnight at 0 ° C. to room temperature did.

MeOH (50 mL) was added and after stirring, it was neutralized with saturated NaHCO ₃ -aq.

It was then extracted with AK-225 (a mixture of CF ₃ CF ₂ CHCl ₂ , CClF ₂ CF ₂ CHClF) and washed with saturated NaCl-aq.

The AK-225 was distilled off with an evaporator to give a yellow powder (124.8 g, 99.1%).

The structure of the obtained yellow powder was confirmed by ¹ H-NMR and ¹⁹ F-NMR.

(result)
¹ H-NMR (Pyridine-d ₅ )
7.158 (4H, s, -O-Ph-O-)
7.16 ~ 7.19 (4H, m, NH- Ph -O-Ph-O- Ph -NH)
7.90 ~ 7.95 (4H, m, NH- Ph -O-Ph-O- Ph -NH)
12.707, 12.726 (2 H, 2 s, NH × 2)
Ph of 7.16 to 7.19 and 7.90 to 7.95 is represented by either of the following formula 12 or formula 13.

¹⁹ F-NMR (Pyridine-d ₅ )
-145.3 (2F, m, -OC F (CF ₃ ) CF ₂ -O- × 2)
-131.1 (2F, m, -OC F (CF ₃ ) CO-NH- × 2)
-129.79, -129.76 (4F, 2s, CF ₃ CF ₂ C F _2- × 2)
-83 to -80 (26 F *, m, C F ₃ C F ₂ CF _2- × 2, -OCF (C F ₃ ) C F _2- O-× 2, -O-CF (C F ₃ ) CO- NH- × 2)
※ Peaks overlap and can not be separated

(Composition example 2)
Synthesis of exemplified compound 1-2 (in the general formula (1), k = 3, m = 1, n = 11, Y is an oxygen atom, and the substitution position is para)

10.1 g of 1,4-bis (4-aminophenoxy) benzene was dissolved in a mixed solvent of 100 mL of pyridine and AK-225 (100 mL), and 209.0 g of acid fluoride (n = 11) was slowly dropped at room temperature . The mixture was stirred at room temperature to 40 ° C. overnight.

MeOH (50 mL) was added and stirred, then neutralized with saturated NaHCO ₃ -aq.

It was then extracted with AK-225 and washed with saturated NaCl-aq.

Subsequently, AK-225 was distilled off with an evaporator to obtain a pale yellow high viscosity liquid (173.9 g, 96.3%). The obtained pale yellow liquid was confirmed for its structure by ¹ H-NMR and ¹⁹ F-NMR.

(result)
¹ H-NMR (Perfluorobenzene / Pyridine-d ₅ = 3/1)
6.93 (4H, d, J = 8.8Hz, NH- Ph -O-Ph-O- Ph -NH)
6.9953 (4H, s, -O-Ph-O-)
7.69 (4H, d, J = 8.6Hz, NH- Ph -O-Ph-O- Ph -NH)
11.9518 (2H, s, NH × 2)
Ph of 6.93 and 7.69 is represented by either of the above Chemical Formula 12 or Chemical Formula 13 as in Synthesis Example 1.

¹⁹ F-NMR (Perfluorobenzene / Pyridine-d ₅ = 3/1)
-143.1 (22 F, m, -OC F (CF ₃ ) CF ₂ -O- × 11 × 2)
-128 ~ -130 (6F, m, -OC F (CF 3) CO-NH- × 2, CF 3 CF 2 C F 2 - × 2)
-78 to -81
(126 F *, m, C F ₃ CF ₂ C F _2- × 2, -OCF (C F ₃ ) C F ₂ -O- × 11 × 2, -O-CF (C F ₃ ) CO-NH- × 2)
※ Peaks overlap and can not be separated

(Composition example 3)
Synthesis of exemplified compound 1-3 (in the general formula (1), k = 3, m = 1, n = 40, Y is an oxygen atom, and the substitution position is para)

2.0 g of 1,4-bis (4-aminophenoxy) benzene was dissolved in a mixed solvent of 100 mL of pyridine and AK-225 (100 mL), and 101.0 g of acid fluoride (n = 40) was slowly dropped at room temperature . The mixture was stirred at room temperature to 40 ° C. overnight.

MeOH (50 mL) was added and stirred, then neutralized with saturated NaHCO ₃ -aq.

It was then extracted with AK-225 and washed with saturated NaCl-aq.

Then, AK-225 was distilled off with an evaporator to obtain a pale yellow high viscosity liquid (97.6 g, 99.6%). The obtained pale yellow liquid was confirmed for its structure by ¹ H-NMR and ¹⁹ F-NMR.

(result)
¹ H-NMR (neat)
6.9 (8H *, m, NH- Ph- O- Ph- O- Ph- NH)
7.3 (4H, m, NH- Ph -O-Ph-O- Ph -NH)
8.0 (2H, br. S, NH x 2)
※ Ph is overlapped and inseparable Ph which is bonded to NH of 6.9 and 7.3 is represented by either of the above-mentioned 12 or 13 as in the synthesis example 1.

¹⁹ F-NMR (neat)
-142 (80 F , m, -OC F (CF ₃ ) CF ₂ -O- x 40 x 2)
-128 ~ -130 (6F, m, -OC F (CF 3) CO-NH- × 2, CF 3 CF 2 C F 2 - × 2)
-77 to -81 (416 F , m, C F ₃ C F ₂ CF _2- × 2, -OCF (C F ₃ ) C F _2- O-× 40 × 2, -O-CF (C F ₃ ) CO -NH- x 2)

(Composition example 4)
Synthesis of Exemplified Compound 1-4 (in the General Formula (1), k = 3, m = 2, n = 1, Y is an oxygen atom, and the substitution position is para) Bis [4- (4-aminophenoxy) phenyl] An ether (25.2 g: in the general formula (3), m = 2, Y is an oxygen atom, and the substitution position is a compound at the para position, CAS No. 13080-88-1) is dissolved in 200 mL of pyridine, and then dissolved on an ice bath Then, 79 g of acid fluoride (n = 1) was slowly dropped, and the mixture was stirred overnight at 0 ° C. to room temperature.

MeOH (50 mL) was added and stirred, then neutralized with saturated NaHCO ₃ -aq.

It was then extracted with AK-225 (a mixture of CF ₃ CF ₂ CHCl ₂ , CClF ₂ CF ₂ CHClF) and washed with saturated NaCl-aq.

Next, AK-225 was distilled off with an evaporator to obtain a pale yellow high viscosity liquid (86.4 g, 98.3%). The structure of the obtained pale yellow high viscosity liquid was confirmed by ¹ H-NMR and ¹⁹ F-NMR.

(result)
¹ H-NMR (Pyridine-d ₅ )
7.159 (8H ※, s, NH -Ph-O- Ph -O- Ph -O-Ph-NH)
7.16 ~ 7.20 (4H, m, NH- Ph -O-Ph-O-Ph-O- Ph -NH)
7.91 ~ 7.94 (4H, m, NH- Ph -O-Ph-O-Ph-O- Ph -NH)
12. 705, 12. 727 (2H, 2s, NH x 2)
* Peaks overlap and can not be separated 7.16 to 7.20 and Ph of 7.91 to 7.94 are represented by either Chemical Formula 12 or Chemical Formula 13 above.

¹⁹ F-NMR (Pyridine-d ₅ )
-145.4 (2F, m, -OC F (CF ₃ ) CF ₂ -O- × 2)
-131.1 (2F, m, -OC F (CF ₃ ) CO-NH- × 2)
-129.78, -129.75 (4F, 2s, CF ₃ CF ₂ C F _2- × 2)
-84 ~ -79 (26F ※, m , C F 3 C F 2 CF 2 - × 2, -OCF (C F 3) C F 2 -0- × 2, -0-CF (C F 3) CO- NH- × 2)
※ Peaks overlap and can not be separated

(Comparative example 1)
Example where the additive of the present invention is not added

Thermal analysis measurement (TG / DTA) of oil "Fombrin M30" was performed. The results are shown in FIG.

As a result, a weight change (TG%) of -10% was observed at a temperature of 390.6 ° C, a rapid change was observed at around 400 ° C, and a change of -100% at 410 ° C (all evaporated, Or guess that it has decomposed and evaporated).

<Measurement conditions>
Sample amount 10 mg
Heating rate 20 ° C / min
Initial temperature 25 ° C
Maximum temperature 500 ° C
No atmosphere gas

Example 1
1 wt% of the product of Synthesis Example 2 was added to the oil “fonbrin M30”, and thermal analysis measurement was performed under the same conditions as Comparative Example 1. The results are shown in FIG.

As a result, at 400 ° C. or less, the change was equivalent to that of no addition (399.5 ° C., −10.1%).

However, there is no sharp change even when the temperature exceeds 400 ° C., which is less than −30% at 450 ° C. and −50% at 500 ° C. The improvement of the heat resistance of the oil was confirmed as compared with the case of no addition.

(Example 2)
3 wt% of the product of Synthesis Example 2 was added to the oil “fonbrin M30”, and thermal analysis measurement was performed under the same conditions as Comparative Example 1. The results are shown in FIG.

As a result, as in Example 1, it was -30% at 450 ° C and -50% at 500 ° C.

Compared with Comparative Example 1 in which the additive of the present invention was not added, improvement in the heat resistance of the oil was confirmed.

(Example 3)
Thermal analysis measurement was performed under the same conditions as Comparative Example 1 using the compound of Synthesis Example 1 in place of the compound of Synthesis Example 2 in Example 1. The results are shown in FIG.

A sharp change was observed around 400 ° C., with a change of −100% at 460 ° C.

(Example 4)
The thermal analysis measurement was performed under the same conditions as Comparative Example 1 using the compound of Synthesis Example 1 in place of the compound of Synthesis Example 2 in Example 2. The results are shown in FIG.

A sharp change was observed around 400 ° C., and a change of −50% at 470 ° C.

(Comparative example 2)
1 wt% of a product of the general formula (1) (k = 3, m = 0, n = 1, Y = oxygen atom, para position) was added to the oil “fonbrin M30” under the same conditions as in Comparative Example 1 Thermal analysis measurement was performed at The results are shown in FIG.

A sharp change was observed around 400 ° C., with a change of −100% at 430 ° C.

Claims (7)

The compound shown by following General formula (1).
General formula (1)

[Wherein, Y represents an oxygen atom (O), a sulfur atom (S), a CO group, an SO group or an SO ₂ group, k is an integer of 1 to 5, and m is an integer of 1 to 10, n is an integer of 1 or more. The substitution position of the two substituents on the phenyl group may be any of ortho, meta and para positions. ] The compound according to claim 1, wherein in the general formula (1), Y is an oxygen atom (O) and m is 1 or 2. The oil additive shown by following General formula (1).
General formula (1)

[Wherein, Y represents an oxygen atom (O), a sulfur atom (S), a CO group, an SO group or an SO ₂ group, k is an integer of 1 to 5, and m is an integer of 1 to 10, n is an integer of 1 or more. The substitution position of the two substituents on the phenyl group may be any of ortho, meta and para positions. ] The oil additive according to claim 3, wherein in the general formula (1), Y is an oxygen atom (O) and m is 1 or 2. The oil additive according to claim 3 or 4, which is an additive of a fluorinated oil. An acid fluoride compound represented by the following general formula (2) and a compound having a diamino group represented by the following general formula (3) are reacted in a pyridine solvent to be represented by the general formula (1) according to claim 1 A synthetic method characterized by synthesizing a compound.
General formula (2)

[Wherein, k is an integer of 1 to 5 and n is an integer of 1 or more. ]
General formula (3)

[Wherein, Y represents an oxygen atom (O), a sulfur atom (S), a CO group, an SO group or an SO ₂ group, and m is an integer of 1 to 10. The substitution position of the two substituents on the phenyl group may be any of ortho, meta and para positions. ] The method according to claim 6, wherein the acid fluoride compound represented by the general formula (2) is an acid fluoride compound represented by the following general formula (4).
General formula (4)

[Wherein, n is an integer of 1 or more. ]

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